The present invention relates to pressure-sensitive adhesives, pressure-sensitive adhesive sheets or films, and hot-melt adhesives. Specifically, the present invention relates to pressure-sensitive adhesives which are useful such as for pressure-sensitive adhesive films which pressure-sensitively adhere to the surfaces of a synthetic resin plate, decorative plywood, metal plate, coated steel plate and the like to protect the surfaces from dust adhesion and scratching. The present invention also relates to pressure-sensitive adhesive sheets and films which are useful such as for masking tapes used for baking coatings on automobiles and the like, and as masking tapes used for solder immersion of printed wiring boards and the like, as well as other uses. The present invention further relates to hot-melt adhesives useful for adhesion of a polyolefin resin, mutual adhesion of rubber, adhesion between different materials such as rubber and metal, and the like.
Conventionally, pressure-sensitive adhesive sheets or films have been used to protect the surface of a coated body, such as a coated body used for working, storage and transportation of building materials, electric insulation, electronic products, and automobiles and the like. Such pressure-sensitive adhesive sheets or films should have excellent pressure-sensitive adhesion and, simultaneously, they should be able to be peeled off easily after use thereof without contaminating the surface of the coated body with the pressure-sensitive adhesive. Recently, pressure-sensitive adhesive sheets or films comprising a substrate made of a polyolefin-based resin are increasingly being used instead of pressure-sensitive adhesive sheets or films comprising a substrate made of a plastic vinyl chloride resin. The pressure-sensitive adhesive sheets or films comprising a substrate made of a polyolefin-based resin that mainly have been used in that manner are those integrally formed by co-extrusion of a pressure-sensitive adhesive layer made of a low crystalline or amorphous pressure-sensitive adhesive such as ethylene vinylacetate copolymer (EVA), low density polyethylene and the like, or a pressure-sensitive adhesive layer made of an elastomer such as styrene-isoprene-styrene block copolymer (SIS), hydrogenated styrene-butadiene-styrene block copolymer (SEBS) and the like, with a substrate. However, the above-mentioned pressure-sensitive adhesive sheets or films have problems in that when they are left under a high temperature environment, a change occurs with the lapse of time, causing an increase in pressure-sensitive adhesion force leading to difficulties when later peeling the adhesive sheet or film from the coated body, leaving behind pressure-sensitive adhesive material as a contaminant on the surface of the body, and the like. Japanese Patent Application Laid-Open (JP-A) No. 4-55488 discloses a pressure-sensitive adhesive sheet or film causing no change with the lapse of time even under high temperature environment, in which a pressure-sensitive adhesive film comprising a pressure-sensitive adhesive layer made of a polyethylene or ethylene/xcex1-olefin copolymer having a density of 0.92 g/cm2 or less and a melt index of 1 to 20 g/10 minutes is formed on one surface of a substrate layer made of a thermoplastic resin. Further, JP-A No. 8-157791 discloses a pressure-sensitive adhesive film composed of a pressure-sensitive adhesive layer made of an ethylene-xcex1-olefin copolymer having a weight-average molecular weight Mw of 5xc3x97104 or more, Mw/Mn of 3 or less in which xe2x80x9cMw/Mnxe2x80x9d is a ratio of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn), a melting peak temperature in DSC analysis of 110xc2x0 C. or more, and a heat of fusion of 100 J/g or less, and a substrate made of another polyolefin-based resin. However, these pressure-sensitive adhesive films have low pressure-sensitive adhesion, and in particular, extremely lowered pressure-sensitive adhesion at lower temperature.
On the other hand, hot-melt adhesives containing EVA and the like have been developed. However, they have disadvantageous properties such as insufficient flexibility, crystalline property, and the like. Therefore, the pressure-sensitive adhesion changes significantly, depending on the temperature of usage. In particular, sufficient pressure-sensitive adhesion is not obtained under a low temperature environment. Further, since an adhesion temperature is required that is not lower than the melting temperature, these hot-melt adhesives are not suitable for a material to be adhered which tends to show thermal deformation.
Further, rubber adhesion complexes, such as used in a tire, conveyer belt, hose, lining product and the like, are produced by laminating un-vulcanized rubber materials and then vulcanizing for adhesion. However, a problem arises in that a strongly adhered rubber adhered complex is not obtained, and this occurs because when the above-mentioned rubber materials are laminated, compatibility between un-vulcanized rubber materials maybe poor, and the vulcanization speeds may vary significantly, and the forms of cross-linking and the like may vary significantly as between the rubber materials, leading to an absence of co-vulcanizing property. Moreover, it is known to use a rubber sheet as a water-proof sheet in the water proofing of concrete buildings and the like. However, since the size of the rubber sheet obtained by molding, vulcanization and the like is limited as compared with a sheet otherwise used for such a purpose in the construction field, a considerable number of rubber sheets have to be added and assembled along the length and breadth directions at the construction site. Conventionally, therefore, many pieces of rubber sheets are spread out at the construction site, and edge portions thereof are overlapped and an adhesive is applied on the edge portions, to adhere the rubber sheets together. As the above-mentioned adhesive, a solvent type polychloroprene adhesive is primarily used. Since an organic solvent is used in the above-mentioned polychloroprene adhesive, the organic solvent is vaporized in execution, causing undesirable effects from the standpoints of safety and hygienics for humans, and environmental protection. On the other hand, an aqueous adhesive prepared by compounding tackifier resin into rubber latex is suggested as an adhesive using no organic solvent; however, this aqueous adhesive has problems in terms of adhesion force in that strong adhesion is not obtained easily and peeling tends to occur. Further, a method is known for mutual adhesion of rubbers in which a plastic material, such as a high-pressure polyethylene, polypropylene, polystyrene and the like, is provided so as to intervene between rubbers to be adhered; however, this method has a drawback in that the flexibility of a rubber-adhered complex is lowered due to hardening of the adhered portion.
Under these circumstances, the present inventors have found that the above-mentioned problems are solved by using a unique olefin-based copolymer having certain specific physical properties and a thermoplastic resin composition obtained by using this olefin-based copolymer.
The present invention relates to a unique pressure-sensitive adhesive comprising a specific polymer which can provide a thermoplastic resin composition having an excellent balance of flexibility, heat-resistance, cold-resistance and weather-resistance. The present invention also relates to an adhesive sheet or film composed of this pressure-sensitive adhesive. The present invention also relates to a unique hot-melt adhesive. More particularly, the present invention relates to a pressure-sensitive adhesive which pressure-sensitively adheres or adheres without using an organic solvent, and also maintains suitable pressure-sensitive adhesion without causing extreme change with the lapse of time, even under a low temperature environment or a high temperature environment and irrespective of the environmental temperature under which a connected article is placed.
Namely, the present invention relates to a pressure-sensitive adhesive comprising an olefin-based copolymer wherein
(1) the olefin-based copolymer has a tensile strength at break measured according to JIS K 6251 of 2.0 MPa or less, and
(2) the elongation at break EB(%) of a resin composition obtained in blending the olefin-based copolymer with a polypropylene-based resin having a 20xc2x0 C. xylene-soluble component content of 20 wt % or less satisfies the following formula 1:
S[2/6]xe2x89xa7xe2x88x92800xe2x80x83xe2x80x83(formula 1)
xe2x80x83wherein, S[2/6] represents the gradient of a primary straight line obtained by approximation according to the least square method of a multiple regression curve in Pa=0.20 to 0.60 region of a multiple regression formula derived by quintet multiple regression of a curve obtained by plotting the elongation at break EB(%) (according to JIS K 6251) of the resin composition on the ordinate and the weight content proportion Pa of the olefin-based copolymer contained in the resin composition on the abscissa wherein, Pa represents the weight content proportion of the olefin-based copolymer contained in the resin composition, and said multiple regression formula essentially includes data at least at seven points of Pa=0.00, 0.20, 0.30, 0.40, 0.50, 0.60 and 0.70, and when further number of points are included, all Pa values are essentially situated mutually at an interval of 0.10 or less.
The present invention also relates to a pressure-sensitive adhesive sheet or film comprising the above-mentioned pressure-sensitive adhesive, and another aspect of the present invention is a hot-melt adhesive comprising the above-mentioned pressure-sensitive adhesive.
The olefin-based copolymer used in the present invention is an olefin-based copolymer having a tensile strength at break measured according to JIS K 6251 of 2.0 MPa or less, preferably 1.8 MPa or less, more preferably 1.6 MPa or less, further preferably 1.4 MPa or less, further more preferably 1.2 MPa or less, still further more preferably 1.0 MPa or less and particularly preferably 0.8 MPa or less. When the tensile strength at break is outside of this range, the resulting olefin-based copolymer and a thermoplastic resin composition containing this olefin-based copolymer are inferior in flexibility, leading to poor pressure-sensitive adhesion force of a pressure-sensitive adhesive comprising this composition, and in the case of use as a hot-melt adhesive, the flexibility of the connected portion becomes poor.
In formula 1, S[2/6] is preferably
S[2/6]xe2x89xa7xe2x88x92800,
more preferably,
xe2x80x83S[2/6]xe2x89xa7xe2x88x92200,
further preferably,
S[2/6]xe2x89xa7xe2x88x92100,
particularly preferably,
S[2/6]xe2x89xa7xe2x88x9250.
When the olefin-based copolymer used in the present invention does not satisfy the relation of formula 1, the resulting olefin-based copolymer and a thermoplastic resin composition containing this olefin-based copolymer are inferior in balancing flexibility, heat-resistance, cold-resistance and weather-resistance; and therefore, the stable pressure-sensitive adhesion force becomes unstable and poor, depending on environmental temperature under which a connected body obtained by using a pressure-sensitive adhesive comprising the copolymer is placed, and in the case of use as a hot-melt adhesive, the flexibility of the connected portion becomes poor.
A multiple regression formula derived by quintet multiple regression of a curve obtained by plotting the elongation at break EB(%) according to JIS K 6251 of the resin composition on the ordinate, and the weight content proportion Pa of the olefin-based copolymer contained in the resin composition plotted on the abscissa is preferably calculated using data at blend composition points where the weight content proportion Pa of the olefin-based copolymer is 0.00, 0.20, 0.30, 0.40, 0.50, 0.60 and 0.70.
The elongation at break EB(%) of the resin composition can be measured according to JIS K 6251, for example, using a dumbbell form No. 3 test piece at a tension speed of 200 mm/min. The number of the test piece was 3, and an arithmetic mean value can be used as the measured result. Herein, for obtaining the measured result of higher accuracy, the number of the test piece is preferably 5 or more, more preferably 7 or more and further preferably 9 or more, and the resulted elongation at break can be arithmetically averaged to give a result to be used. For removing the result of irregular low elongation at break, it is preferable to delete results revealing tensile strength at break which is 80% or less of the median of the measured results or of the average of two values surrounding the median, and to arithmetically average the remaining measured results to give a result to be used.
For blending an olefin-based copolymer with a polypropylene-based resin having a 20xc2x0 C. xylene-soluble component content of 20 wt % or less, the components may be advantageously kneaded using a usual kneading apparatus, for example, a rubber mill, Brabender mill, Banbury mixer, press kneader, ruder, twin-screw extruder and the like. The kneading temperature is a temperature at which all of mixed components are melted, and usually from 160 to 250xc2x0 C., preferably from 180 to 240xc2x0 C. The resulted resin composition is press-molded to the defined thickness by a method according to JIS K 6758, to give a sample of the tensile test.
The above-mentioned quintet multiple regression can be calculated, for example, by methods shown in xe2x80x9cKagakusha oyobi Kagaku Gijutsusha no tameno Toukeiteki Houhou (Statistical method for chemist and chemical engineer)xe2x80x9d (sec. Ed.) (pub. Tokyo Kagaku Dojin K.K.) chapters 6.3 and 6.4. The multiple correlation coefficient R and the gradient S obtained by straight line regression using the least square method can be calculated, for example, by methods shown in xe2x80x9cKagakusha oyobi Kagaku Gijutsusha no tameno Toukeiteki Houhou (Statistical method for chemist and chemical engineer)xe2x80x9d (sec. Ed.) (pub. Tokyo Kagaku Dojin K.K.) chapters 6.3 and 6.4.
In the olefin-based copolymer used in the present invention, it is further preferable that the relation of the following formula 2 is satisfied in addition to the above-mentioned relation, from the standpoint of stability of surface nature and condition of a resin composition,
R[3/5]xe2x88x92R[2/6]xe2x89xa70.15xe2x80x83xe2x80x83formula 2
wherein, R[3/5] and R[2/6] represent the multiple correlation coefficients of primary straight lines obtained by approximation according to the least square method of multiple regression curves in Pa=0.30 to 0.50 and Pa=0.20 to 0.60 regions of a multiple regression formula derived by quintet multiple regression of a curve obtained by plotting the elongation at break EB(%) according to JIS K 6251 of the resin composition on the ordinate and the weight content proportion Pa of the olefin-based copolymer contained in the resin composition on the abscissa wherein, Pa represents the weight content proportion of the olefin-based copolymer contained in the resin composition. Herein, said multiple regression formula essentially includes data at least at seven points of Pa=0.00, 0.20, 0.30, 0.40, 0.50, 0.60 and 0.70, and when an additional number of points are included, all Pa values are essentially situated mutually at an interval of 0.10 or less.
In this relation, R[3/5] and R[2/6] are preferably
R[3/5]xe2x88x92R[2/6]xe2x89xa70.20,
more preferably,
R[3/5]xe2x88x92R[2/6]xe2x89xa70.25,
further preferably,
R[3/5]xe2x88x92R[2/6]xe2x89xa70.30,
particularly preferably,
R[3/5]xe2x88x92R[2/6]xe2x89xa70.35,
most preferably,
R[3/5]xe2x88x92R[2/6]xe2x89xa70.40.
When the olefin-based copolymer used in the present invention does not satisfy the relations of formula 1 and formula 2, the resulting thermoplastic resin composition may have inferior surface stability in terms of surface nature and condition, such as manifested as bleeding on the surface with the lapse of time, and the like. Therefore, stable pressure-sensitive adhesion force with the lapse of time may not be obtained, depending on the environmental temperature under which a connected body obtained by using a pressure-sensitive adhesive comprising the copolymer is placed. On the other hand, in the case of use for a pressure-sensitive adhesive sheet or film, there is a concern about the occurrence of problems such as a pressure-sensitive component remaining as a contaminant on the surface after its release from a body, and the like.
In the olefin-based copolymer used in the present invention, it is further preferable that the relation of the following formula 3 is satisfied in addition to the above-mentioned relation from the standpoint of stability of the surface nature and condition of the resin composition,
S[3/5]xe2x88x92S[2/6]xe2x89xa6xe2x88x9250xe2x80x83xe2x80x83formula 3
wherein, S[3/5] and S[2/6] represent the gradients of primary straight lines obtained by approximation according to the least square method of multiple regression curves in Pa=0.30 to 0.50 and Pa=0.20 to 0.60 regions of a multiple regression formula derived by quintet multiple regression of a curve obtained by plotting the elongation at break EB(%) according to JIS K 6251 of the resin composition on the ordinate and the weight content proportion Pa of the olefin-based copolymer contained in the resin composition on the abscissa wherein, Pa represents the weight content proportion of the olefin-based copolymer contained in the resin composition.
In this relation, S[3/5] and S[2/6] are preferably
S[3/5]xe2x88x92S[2/6]xe2x89xa6xe2x88x9270,
more preferably,
S[3/5]xe2x88x92S[2/6]xe2x89xa6xe2x88x9290,
particularly preferably,
S[3/5]xe2x88x92S[2/6]xe2x89xa6xe2x88x92110,
most preferably,
S[3/5]xe2x88x92S[2/6]xe2x89xa6xe2x88x92120.
When the olefin-based copolymer used in the present invention does not satisfy the relations of formula 2 and formula 3, the resulting olefin-based copolymer and a thermoplastic resin composition containing this olefin-based copolymer may have a poor balance of flexibility, heat-resistance, cold-resistance and weather-resistance, and a poor surface stability in terms of surface nature and condition. Therefore, stable pressure-sensitive adhesion force may not be obtained, depending on environmental temperature under which a connected body obtained by using a pressure-sensitive adhesive comprising the copolymer is placed.
The polypropylene-based resin having a 20xc2x0 C. xylene-soluble component content of 20 wt % or less described in (2) in the present invention is a polypropylene-based resin (X) which is selected from polypropylene-based resins described in (i-4) below and satisfies the following requirements described later. The 20xc2x0 C. xylene-soluble component content of the polypropylene-based resin means a numerical value obtained according to the following methods and conditions. Namely, about 200 mg of a polypropylene-based resin is weighed and mixed with 100 ml of xylene, and the resin is dissolved for 50 minutes while boiling xylene. After given time, the solution was left to cool for 20 minutes at room temperature, then, the polypropylene-based resin was crystallized with 0xc2x0 C. ice water. Then, the mixture was kept for 1 hour in a constant temperature water bath at 20xc2x0 C. Then, the xylene-soluble component is separated through a filter from the xylene-insoluble component, the xylene-insoluble component is dried by a vacuum drier to constant weight, the dried xylene-insoluble component is weighed, and the weight of the xylene-soluble component is calculated based the weight difference from the original sample. The xylene-soluble component content is represented in terms of percentage (wt %) of the weight of the xylene-soluble component based on the weight of the original sample.
In the polypropylene-based resin (X) having a 20xc2x0 C. xylene-soluble component content of 20 wt % or less, it is preferable that the crystallization temperature Tc (xc2x0 C.) and the crystallization heat xcex94H (mj/mg) measured by using a differential scanning calorimeter (DSC) satisfy the following relation. Measurement of DSC is conducted, for example, using DSC 220C manufactured by Seiko Instruments Inc. at a speed of 10xc2x0 C./min. of temperature raising and lowering processes, according to JIS K 7121 and JIS K 7122.
xe2x88x9210xe2x89xa6[xcex94Hxe2x88x92(Tcxc3x971.4)xe2x88x9262]xe2x89xa610
More preferably
xe2x88x928xe2x89xa6[xcex94Hxe2x88x92(Tcxc3x971.4)xc3x9762]xe2x89xa68
Further preferably
xe2x88x926xe2x89xa6[xcex94Hxe2x88x92(Tcxc3x971.4)xe2x88x9262]xe2x89xa66
When the polypropylene-based resin (X) having a 20xc2x0 C. xylene-soluble component content of 20 wt % or less does not satisfy the above-mentioned relation, it may be impossible to correctly determine a specific olefin-based copolymer which can provide a thermoplastic resin composition having excellent balance of flexibility, heat-resistance, cold-resistance, weather-resistance and stability of surface nature and condition.
The polypropylene-based resin (X) having a 20xc2x0 C. xylene-soluble component content of 20 wt % or less is preferably crystalline polypropylene mainly having isotactic or syndiotactic sequence structure of homo type or of random type containing a comonomer, more preferably a polypropylene-based resin of random type containing a comonomer. This polypropylene-based resin can be obtained by adopting a gas phase polymerization method, bulk polymerization method or solvent polymerization method, and the number-average molecular weight of the polymer is not particularly restricted and preferably is controlled from 10,000 to 1,000,000.
For obtaining the polypropylene-based resin (X) having a 20xc2x0 C. xylene-soluble component content of 20 wt % or less, there are generally listed methods in which a homopolymer of propylene is obtained or a copolymer is obtained by copolymerizing propylene with one or more olefins selected from olefins having 2 to 12 carbon atoms other than the propylene, by a slurry polymerization, gas phase polymerization or bulk polymerization method using what is called a Ziegler-Natta catalyst combining a titanium-containing solid transition metal component and an organometal component, or a metallocene catalyst comprising a compound of a transition metal of group IV to group VI of the periodic table having at least one cyclopentadienyl skeleton and a co-catalyst component. Further, commercially available products corresponding to the resins produced as described above can also be used.
When the above-mentioned parameters are not satisfied, the resulting olefin-based copolymer and a thermoplastic resin composition containing this olefin-based copolymer may be inferior in the balance of flexibility, heat-resistance, cold-resistance and weather-resistance; and, therefore, stable pressure-sensitive adhesion force may not be obtained, depending on environmental temperature under which a connected body obtained by using a pressure-sensitive adhesive comprising the copolymer is placed.
Further, from the standpoint of the flexibility of the olefin-based copolymer and thermoplastic resin composition containing this olefin-based copolymer used in the present invention, it is preferable that the following property is satisfied in addition to the above-mentioned property. Namely, in the olefin-based copolymer used in the present invention, it is preferable that the bending modulus (Ua(MPa)) of a thermoplastic resin composition obtained by blending with a homopolypropylene resin, measured according to JIS K 7203, satisfies the relation of the following formula.
Uaxe2x89xa61.5xc3x97Saxc3x97(Ta/100)3.3
More preferably
Uaxe2x89xa61.4xc3x97Saxc3x97(Ta/100)3.3
Further preferably
Uaxe2x89xa61.3xc3x97Saxc3x97(Ta/100)3.3
Particularly preferably
Uaxe2x89xa61.2xc3x97Saxc3x97(Ta/100)3.3
When the bending modulus is outside the above-described range, the resulting olefin-based copolymer and a thermoplastic resin composition containing this olefin-based copolymer may be poor, consequently, the pressure-sensitive adhesion force of a pressure-sensitive adhesive comprising the copolymer may be poor. In the above-described formula, Ua represents the bending modulus (MPa) measured according to JIS K 7203 of the homopolypropylene resin used for blending, and Ta represents the weight (wt %) added of the homopolypropylene resin in the thermoplastic resin composition.
The olefin-based copolymer used in the present invention relates to a copolymer obtained by copolymerizing two or more monomer components selected from ethylene, xcex1-olefin having 3 to 20 carbon atoms, polyene compound, cyclic olefin and vinyl aromatic compound, or a polymer obtained by homopolymerization using these monomers and the polymer has a structure corresponding to the copolymer. Specific examples of the monomers constituting this olefin-based copolymer include the following monomers (a) to (d).
(a) xcex1-olefin
The xcex1-olefin having 3 to 20 carbon atoms used in the present invention includes linear and branched xcex1-olefins, and examples of the linear xcex1-olefin include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nanodecene, 1-eicosene and the like, and examples of the branched xcex1-olefin include 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-hexene, 2,2,4-trimethyl-1-pentene and the like, and linear propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene and the like are preferable.
(b) Polyene Compound
The polyene compound suitably used in the present invention include what is called a conjugated polyene compound having one single bond sandwiched between double bonds, and non-conjugated polyene compounds other than the aforesaid conjugated polyene compound. As the conjugated polyene compound, aliphatic conjugated polyene compounds, alicyclic conjugated polyene compounds, and the like are listed. The aliphatic conjugated polyene compound include linear aliphatic polyene compounds and branched aliphatic polyene compounds. Further, the aliphatic conjugated polyene compound and alicyclic conjugated polyene compound may contain an alkoxy group, aryl group, aryloxy group, aralkyl group, aralkyloxy group and the like. Examples of the aliphatic conjugated polyene compound include 1,3-butadiene, isoprene, 2-ethyl-1,3-butadiene, 2-propyl-1,3-butadiene, 2-isopropyl-1,3-butadiene, 2-hexyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 2-methyl-1,3-hexadiene, 2-methyl-1,3-octadiene, 2-methyl-1,3-decadiene, 2,3-dimethyl-1,3-pentadiene, 2,3-dimethyl-1,3-hexadiene, 2,3-dimethyl-1,3-octadiene, 2,3-dimethyl-1,3-decadiene and the like. Examples of the alicyclic polyene compounds include 2-methyl-1,3-cyclopentadiene, 2-methyl-1,3-cyclohexadiene, 2,3-dimethyl-1,3-cyclopentadiene, 2,3-dimethyl-1,3-cyclohexadiene, 2-chloro-1,3-butadiene, 2,3-dichloro-1,3-butadiene, 1-fluoro-1,3-butadiene, 2-chloro-1,3-pentadiene, 2-chloro-1,3-cyclopentadiene, 2-chloro-1,3-cyclohexadiene and the like.
As the non-conjugated polyene compound, aliphatic non-conjugated polyene compounds, alicyclic non-conjugated polyene compounds, aromatic non-conjugated polyene compounds and the like are listed. The aliphatic non-conjugated polyene compound include linear aliphatic non-conjugated polyene compounds and branched aliphatic non-conjugated polyene compounds. Further, the aliphatic non-conjugated polyene compound, alicyclic non-conjugated polyene compound and aromatic non-conjugated polyene compound may contain an alkoxy group, aryl group, aryloxy group, aralkyl group, aralkyloxy group and the like. Examples of the aliphatic non-conjugated polyene compound include 1,4-hexadiene, 1,5-hexadiene, 1,6-heptadiene, 1,6-octadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,13-tetradecadiene, 1,5,9-decatriene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4-ethyl-1,4-hexadiene, 3-methyl-1,5-hexadiene, 3,3-dimethyl-1,4-hexadiene, 3,4-dimethyl-1,5-hexadiene, 5-methyl-1,4-heptadiene, 5-ethyl-1,4-heptadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 5-ethyl-1,5-heptadiene, 3-methyl-1,6-heptadiene, 4-methyl-1,6-heptadiene, 4,4-dimethyl-1,6-heptadiene, 4-ethyl-1,6-heptadiene, 4-methyl-1,4-octadiene, 5-methyl-1,4-octadiene, 4-ethyl-1,4-octadiene, 5-ethyl-1,4-octadiene, 5-methyl-1,5-octadiene, 6-methyl-1,5-octadiene, 5-ethyl-1,5-octadiene, 6-ethyl-1,5-octadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 6-ethyl-1,6-octadiene, 6-propyl-1,6-octadiene, 6-butyl-1,6-octadiene, 4-methyl-1,4-nonadiene, 5-methyl-1,4-nonadiene, 4-ethyl-1,4-nonadiene, 5-ethyl-1,4-nonadiene, 5-methyl-1,5-nonadiene, 6-methyl-1,5-nonadiene, 5-ethyl-1,5-nonadiene, 6-ethyl-1,5-nonadiene, 6-methyl-1,6-nonadiene, 7-methyl-1,6-nonadiene, 6-ethyl-1,6-nonadiene, 7-ethyl-1,6-nonadiene, 7-methyl-1,7-nonadiene, 8-methyl-1,7-nonadiene, 7-ethyl-1,7-nonadiene, 5-methyl-1,4-decadiene, 5-ethyl-1,4-dicadiene, 5-methyl-1,5-decadiene, 6-methyl-1,5-decadiene, 5-ethyl-1,5-decadiene, 6-ethyl-1,5-decadiene, 6-methyl-1,6-decadiene, 6-ethyl-1,6-decadiene, 7-methyl-1,6-decadiene, 7-ethyl-1,6-decadiene, 7-methyl-1,7-decadiene, 8-methyl-1,7-decadiene, 7-ethyl-1,7-decadiene, 8-ethyl-1,7-decadiene, 8-methyl-1,8-decadiene, 9-methyl-1,8-decadiene, 8-ethyl-1,8-decadiene, 6-methyl-1,6-undecadiene, 9-methyl-1,8-undecadiene, 6,10-dimethyl-1,5,9-undecatriene, 5,9-dimethyl-1,4,8-decatriene, 4-ethylidene-8-methyl-1,7-nonadiene, 13-ethyl-9-methyl-1,9,12-pentadecatriene, 5,9,13-trimethyl-1,4,8,12-tetradecatetraene, 8,14,16-trimethyl-1,7,14-hexadecatriene, 4-ethylidene-12-methyl-1,11-pentadecadiene and the like. Examples of the alicyclic non-conjugated polyene compound include vinylcyclohexene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropenyl-2-norbornene, cyclohexadiene, dicyclopentadiene, cyclooctadiene, 2,5-norbornadiene, 2-methyl-2,5-norbornadiene, 2-ethyl-2,5-norbornadiene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, 1,4-divinylcyclohexane, 1,3-divinylcyclohexane, 1,5-divinylcyclooctane, 1-allyl-4-vinylcyclohexane, 1,4-diallylcyclohexane, 1-allyl-5-vinylcyclooctane, 1,5-diallylcyclooctane, 1-allyl-4-isopropenylcyclohexane, 1-isopropenyl-4-vinylcyclohexane, 1-isopropenyl-3-vinylcyclopentane, methyltetrahydroindene and the like. Examples of the aromatic non-conjugated polyene compound include divinylbenzene, vinylisopropenylbenzene and the like.
(c) Cyclic Olefin Compound
Examples of the cyclic olefin constituting the olefin-based copolymer used in the present invention include norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5,6-dimethylnorbornene, 1-methylnorbornene, 7-methylnorbornene, 5,5,6-trimethylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, 5-ethylidenenorbornene, 5-vinylnorbornene, 1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-ethyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-hexyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-ethylidene-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-fluoro-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 1,5-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-cyclohexyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2,3-dichloro-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-isobutyl-1,4,5,8-dimethanol-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 1,2-dihydrodicyclopentadiene, 5-chloronorbornene, 5,5-dichloronorbornene, 5-fluoronorbornene, 5,5,6-trifluoro-6-trifluoromethylnorbornene, 5-chloromethylnorbornene, 5-methoxynorbornene, 5,6-dicarboxynorborneneanhydride, 5-dimethylamino-norbornene, 5-cyclonorbornene, cyclopentene, 3-methylcyclo-pentene, 4-methylcyclopentene, 3,4-dimethylcyclopentene, 3,5-dimethylcyclopentene, 3-chlorocyclopentene, cyclohexene, 3-methylcyclohexene, 4-methylcyclohexene, 3,4-dimethylcyclohexene, 3-chlorocyclohexene, cycloheptene and the like.
(d) Vinyl Aromatic Compound
Examples of the vinyl aromatic compound which can be used in constituting the olefin-based copolymer used in the present invention include styrene, xcex1-methylstyrene, p-methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, p-tert-butylstyrene, ethylstyrene, vinylnaphthalene and the like.
Further, in the present invention, from the standpoint of stable pressure-sensitive adhesion force to an article to be adhered, which is one of objects of the present invention, it is preferable to use a polymer composed of a specific combination of monomers selected from the above-mentioned monomers, and preferable examples thereof include the following combinations {circle around (1)} to {circle around (19)}.
{circle around (1)} Olefin-based copolymers obtained by copolymerizing ethylene and an xcex1-olefin having 3 to 20 carbon atoms as essential components, and optionally, one or more monomer components selected from polyene compounds, cyclic olefins and vinyl aromatic compounds.
{circle around (2)} Olefin-based copolymers obtained by copolymerizing ethylene and an xcex1-olefin having 4 to 20 carbon atoms as essential components, and optionally, one or more monomer components selected from polyene compounds, cyclic olefins and vinyl aromatic compounds.
{circle around (3)} Olefin-based copolymers obtained by copolymerizing ethylene, propylene and an xcex1-olefin having 4 to 20 carbon atoms as essential components, and optionally, one or more monomer components selected from polyene compounds, cyclic olefins and vinyl aromatic compounds.
{circle around (4)} Olefin-based copolymers obtained by copolymerizing propylene and an xcex1-olefin having 4 to 20 carbon atoms as essential components, and optionally, one or more monomer components selected from polyene compounds, cyclic olefins and vinyl aromatic compounds.
{circle around (5)} Olefin-based copolymers composed of ethylene and an xcex1-olefin having 4 to 20 carbon atoms.
{circle around (6)} Olefin-based copolymers composed of ethylene, an xcex1-olefin having 4 to 20 carbon atoms and a polyene compound.
{circle around (7)} Olefin-based copolymers composed of ethylene, an xcex1-olefin having 4 to 20 carbon atoms and acyclic olefin compound.
{circle around (8)} Olefin-based copolymers composed of ethylene, an xcex1-olefin having 4 to 20 carbon atoms and a vinyl aromatic compound.
{circle around (9)} Olefin-based copolymers composed of ethylene, an xcex1-olefin having 4 to 20 carbon atoms, a polyene compound and a vinyl aromatic compound.
{circle around (10)} Olefin-based copolymers composed of ethylene, propylene and an xcex1-olefin having 4 to 20 carbon atoms.
{circle around (11)} Olefin-based copolymers composed of ethylene, propylene, an xcex1-olefin having 4 to 20 carbon atoms and a polyene compound.
{circle around (12)} Olefin-based copolymers composed of ethylene, propylene, an xcex1-olefin having 4 to 20 carbon atoms and a cyclic olefin compound.
{circle around (13)} Olefin-based copolymers composed of ethylene, propylene, an xcex1-olefin having 4 to 20 carbon atoms and a vinyl aromatic compound.
{circle around (14)} Olefin-based copolymers composed of ethylene, propylene, an xcex1-olefin having 4 to 20 carbon atoms, a polyene compound and a vinyl aromatic compound.
{circle around (15)} Olefin-based copolymers composed of propylene and an xcex1-olefin having 4 to 20 carbon atoms.
{circle around (16)} Olefin-based copolymers composed of propylene, an xcex1-olefin having 4 to 20 carbon atoms and a polyene compound.
{circle around (17)} Olefin-based copolymers composed of propylene, an xcex1-olefin having 4 to 20 carbon atoms and acyclic olefin compound.
{circle around (18)} Olefin-based copolymers composed of propylene, an xcex1-olefin having 4 to 20 carbon atoms and a vinyl aromatic compound.
{circle around (19)} Olefin-based copolymers composed of propylene, an xcex1-olefin having 4 to 20 carbon atoms, a polyene compound and a vinyl aromatic compound.
Of the above-mentioned combinations, the following combinations are preferably used, from the standpoint that the pressure-sensitive adhesive of the present invention has stable pressure-sensitive adhesion force particularly under lower temperature environment.
{circle around (2)} Olefin-based copolymers obtained by copolymerizing ethylene and an xcex1-olefin having 4 to 20 carbon atoms as essential components, and optionally, one or more monomer components selected from polyene compounds, cyclic olefins and vinyl aromatic compounds.
{circle around (3)} Olefin-based copolymers obtained by copolymerizing ethylene, propylene and an xcex1-olefin having 4 to 20 carbon atoms as essential components, and optionally, one or more monomer components selected from polyene compounds, cyclic olefins and vinyl aromatic compounds.
Of the above-mentioned combinations, the following combinations are preferably used, from the standpoint that the pressure-sensitive adhesive of the present invention has weather-resistance.
{circle around (5)} Olefin-based copolymers composed of ethylene, an xcex1-olefin having 4 to 20 carbon atoms, a polyene compound and a vinyl aromatic compound.
{circle around (10)} Olefin-based copolymers composed of ethylene, propylene and an xcex1-olefin having 4 to 20 carbon atoms.
Further, it is preferable that the olefin-based copolymer used in the present invention has neither a peak of 1 J/g or more based on melting of a crystal nor a peak of 1 J/g or more based on crystallization, when measured according to JIS K 7122 using a differential scanning calorimeter (DSC). Moreover, the olefin-based copolymer used in the present invention has a glass transition temperature (Tg) of preferably xe2x88x9210xc2x0 C. or less, more preferably xe2x88x9220xc2x0 C. or less, and particularly preferably xe2x88x9225xc2x0 C. or less. When this condition is not satisfied, an pressure-sensitive adhesive comprising the copolymer may be inferior in stable press-sensitive adhesion force under lower temperature environments, and in the case of use as a hot-melt adhesive, the flexibility of a connected portion may be poor.
As the differential scanning calorimeter, there is used, for example, a DSC 220C manufactured by Seiko Instruments Inc., and the measuring speed is 10xc2x0 C./min. in temperature raising and lowering processes.
The olefin-based copolymer used in the present invention has a molecular weight distribution (Mw/Mn) measured by gel permeation chromatography (GPC) of preferably 5 or less, more preferably 4 or less and further preferably 3 or less. When the molecular weight distribution is too wide, bleed out of lower molecular weight components may increase, and a pressure-sensitive adhesive comprising the copolymer may not have sufficient stable pressure-sensitive adhesion force particularly under high temperature environments, and may tend to contaminate the surface of an article to be adhered after use.
Measurement of the molecular weight distribution is conducted by a gel permeation chromatography (GPC) method, for example, using 150C/GPC apparatus, manufactured by Waters Co. The elution temperature is 140xc2x0 C., and for example, a Shodex Packed Column A-80M manufactured by Showa Denko K.K. is used as a column, and polystyrene, for example, manufactured by Tosoh. Corp., having a molecular weight 68 to 8,400,000 is used as a molecular weight standard substance. The weight-average molecular weight (Mw) and the number-average molecular weight (Mn) are obtained in terms of polystyrene, and this ratio (Mw/Mn) is called molecular weight distribution. About 5 mg of a polymer is dissolved in 5 ml of o-dichlorobenzene to prepare a measuring sample having a concentration of about 1 mg/ml. 400 xcexcl of the resulted sample solution is injected, elution solvent flow rate is controlled to 1.0 ml/min., and detection is conducted by a refractive index detector.
The olefin-based copolymer used in the present invention has an intrinsic viscosity [xcex7] obtained by using a tetralin solvent at 135xc2x0 C. of preferably from 0.1 to 10.0 dl/g, more preferably from 0.2 to 7.0 dl/g, and further preferably from 0.3 to 5.0 dl/g. When this intrinsic viscosity is too low, the heat-resistance of the resulting olefin-based copolymer may be inferior, and therefore, a pressure-sensitive adhesive comprising the copolymer may have poor pressure-sensitive adhesion force, particularly under a high temperature environment. On the other hand, when the intrinsic viscosity is too high, the resulting olefin-based copolymer may be poor in flexibility, and therefore, a pressure-sensitive adhesive comprising the copolymer may have poor pressure-sensitive adhesion force.
The intrinsic viscosity [xcex7] is measured by using an Ubbellohde viscometer in tetralin at 135xc2x0 C. 300 mg of the sample is dissolved in 100 ml of tetralin to prepare a 3 mg/ml solution. Further, this solution is diluted 2-fold, 3-fold and 5-fold, and the intrinsic viscosity of each of them is measured in a constant temperature oil bath at 135xc2x0 C. (xc2x10.1xc2x0 C.). The measurement is repeated three times at each concentration, and the resulted values are averaged for use.
The olefin-based copolymer used in the present invention can be produced by using a known Ziegler-Natta catalyst or a known single site catalyst such as metallocene type, and the like. From the standpoint of uniformity of the composition distribution of the resulting polymer, a known single site catalyst such as metallocene type, and the like is preferable. Examples of this single site catalyst include metallocene type catalysts described, for example, in Japanese Patent Application Laid-Open (JP-A) Nos. 58-19309, 60-35005, 60-35006, 60-35007, 60-35008, 61-130314, 3-163088, 4-268307, 9-12790, 9-87313, 10-508055, 11-80233, and the like, and non-metallocene type complex catalysts described in JP-A Nos. 10-316710, 11-100394, 11-80228, 11-80227, 10-513489, 10-338706 and 11-71420. Among them, metallocene catalysts are generally used, and as suitable metallocene catalyst example, it is preferable to use a transition metal complex of group III to group XII of the periodic table which has at least one cyclopentadiene-type anion skeleton and has C1 symmetric structure from the standpoint of the flexibility of the resulting polymer. Further, the method described in Japanese Patent Application No. 11-206054 can be exemplified as a suitable example of the production method using a metallocene catalyst in obtaining a polymer having higher molecular weight.
Subsequently, a thermoplastic resin composition comprises a unique olefin-based copolymer used in the present invention and such a thermoplastic resin composition is also described herein.
The thermoplastic resin composition used in the present invention is a thermoplastic resin composition comprising (i) a thermoplastic resin, and (ii) the olefin-based copolymer used in the present invention, as essential components. The used amounts of them are not particularly restricted, however, from the standpoints of flexibility and heat-resistance, the ratio by weight of a thermoplastic resin to an olefin-based copolymer is preferably from 1/99 to 95/5, more preferably from 3/97 to 90/10, particularly preferably from 5/95 to 80/20.
The component (i) used in the thermoplastic resin composition of the present invention is a thermoplastic resin. The component (i) can be widely selected from known various thermoplastic resins, and examples thereof include, for example, polyethylene-based resins such as a high density polyethylene, middle density polyethylene, low density polyethylene, linear low density polyethylene (LLDPE) and the like; polypropylene-based resin, polybutene-based resins, poly-4-methyl-pentene-1-based resins, polystyrene-based resins, polyester-based resins, polyamide-based resins, polyphenylene ether-based resins, polyphenylene oxide resins, polyacetal-based resins, polycarbonate-based resins and the like. As to component (i), (i-1) polyolefin-based resins are preferable; (i-2) polyolefin-based resins mainly composed of aliphatic olefins having 2 or more carbon atoms are more preferable; (i-3) polyolefin-based resins mainly composed of aliphatic olefins having 3 or more carbon atoms are further preferable; and (i-4) polypropylene-based resins are particularly preferable.
As the polypropylene-based resin (i-4), there can be used crystalline polypropylene mainly having isotactic or syndiotactic sequence structure of homo type or of random type containing a comonomer, or those having various structures such as block polypropylene obtained by multi-stage polymerization. This polypropylene-based resin can be obtained by adopting a gas phase polymerization method, bulk polymerization method, solvent polymerization method or multi-stage polymerization method combining them. The number-average molecular weight of the polymer is not particularly restricted and preferably is controlled from 10,000 to 1,000,000.
As the index of the crystallinity of the polypropylene-based resin (i-4), for example, melting point, crystal melting calorie and the like are used, and it is preferable that the melting point is from 80xc2x0 C. to 176xc2x0 C. and the crystal melting calorie is from 30 J/g to 120 J/g. It is further preferable that the melting point is from 120xc2x0 C. to 176xc2x0 C. and the crystal melting calorie is from 60 J/g to 120 J/g. When the melting point of a crystal is too low or the melting calorie is too low, the heat-resistance of the resulting thermoplastic resin composition may decrease, consequently, the pressure-sensitive adhesion force under a high temperature environment of a pressure-sensitive adhesive containing the aforesaid composition may decrease.
For producing the polypropylene-based resin (i-4), useful methods generally include those in which a homopolymer is obtained by homopolymerization of propylene via one stage or multi stages, or a copolymer is obtained by copolymerizing propylene with one or more olefins selected from olefins having 2 to 12 carbon atoms other than the propylene via one stage or multi stages, in a slurry polymerization, gas phase polymerization, bulk polymerization or a solution polymerization method or a polymerization method combining them, using a Ziegler-Natta catalyst combining a titanium-containing solid transition metal component and an organometal component, or a metallocene catalyst comprising a compound of a transition metal of group IV to group VI of the periodic table having at least one cyclopentadienyl skeleton and a co-catalyst component. Further, commercially available products can also be used.
In the thermoplastic resin composition used in the present invention, it is preferable that the bending modulus (Ub(MPa)) measured according to JIS K 7203 satisfies the relation of the following formula.
Ubxe2x89xa61.5xc3x97Sbxc3x97(Tb/100)3.3
More preferably
Ubxe2x89xa61.4xc3x97Sbxc3x97(Tb/100)3.3
Further preferably
Ubxe2x89xa61.3xc3x97Sbxc3x97(Tb/100)3.3
Particularly preferably
Ubxe2x89xa61.2xc3x97Sbxc3x97(Tb/100)3.3
When the bending modulus is out of the above-described range, the thermoplastic resin composition may be inferior in flexibility, and, consequently, the resulting pressure-sensitive adhesive may have poor pressure-sensitive adhesion force. In the above-described formula, Ub represents the bending modulus (MPa) measured according to JIS K 7203, and Tb represents the added parts (%) of the thermoplastic resin composition.
In the olefin-based copolymer used in the present invention and a thermoplastic resin composition containing this olefin-based copolymer, known thermoplastic resins, rubber, and other components can be selected and compounded appropriately, if necessary, within a range wherein the object of the present invention does not deteriorate, and the thermoplastic resin composition used in the present invention may also be a thermoplastic resin composition comprising (i) a thermoplastic resin, (ii) a olefin-based copolymer used in the present invention and (iii) other elastomer, as essential components. In the component (i), the thermoplastic resin can be selected for use from various ethylene-based resins, various polypropylene-based resins, various polybutene-based resins, various polymethylpentene-based resins, polystyrene-based resins, copolymer resins of ethylene with acrylic monomers, copolymer resins of ethylene with vinyl acetate-based monomers, copolymer resins of ethylene with methacrylic monomers, acrylic resins, polyester-based resins, polycarbonate-based resins, nylon-based resins, polyvinyl alcohol-based resins and the like. As (iii), the other elastomer, there are exemplified ethylene/xcex1-olefin-based copolymer rubber, ethylene/xcex1-olefin/polyene-based copolymer rubber; and styrene-based rubber such as styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), hydrogenated styrene-isoprene-styrene block copolymer (SPES), hydrogenated styrene-butadiene-styrene block copolymer (SEBS) and the like; diene-based rubber, known cross-linking rubber. And if necessary, other components can also be added to these components, and examples of these components which can be added include rosin-based resins, polyterpene-based resins, synthetic petroleum resins, cumarone-based resins, phenol-based resins, xylene-based resins, isoprene-based resins and the like.
In the olefin-based copolymer used in the present invention and a thermoplastic resin composition containing this olefin-based copolymer, if necessary, cross-linking can also be conducted such as sulfur cross-linking, peroxide cross-linking, metal ion cross-linking, silane cross-linking, resin cross-linking and the like according to conventionally known methods. As the cross-linking agent, there can be used cross-linking agents generally used for vulcanization of rubber, and there can be exemplified cross-linking agents such as sulfur, phenols resins, metal oxides, metal hydroxides, metal chlorides, p-quinonedioxime or bismaleimide-based cross-linking agents and the like. The cross-linking agent can be used alone, and for controlling the cross-linking speed, a cross-linking promoter may also be used together. As the cross-linking promoter, there can be used oxidizing agents such as red lead, dibenzothiazoyl sulfide and the like. Further, a metal oxide such as zinc oxide or the like, stearic acid and the like can also be used together as a dispersing agent. As the metal oxide, zinc oxide, magnesium oxide, lead oxide, calcium oxide and the like can be used, and zinc oxide or magnesium oxide is preferable. Further, the thermoplastic resin composition used in the present invention can be dynamically cross-linked in the presence of a cross-linking agent to obtain a cross-linked substance.
For obtaining the thermoplastic resin composition used in the present invention, the components as explained above may be advantageously kneaded using a usual kneading apparatus, for example, a rubber mill, Brabender mill, Banbury mixer, press kneader, ruder, twin-screw extruder and the like. The kneading apparatus may be any of closed type and open type apparatuses, and a closed type apparatus in which inert gas purging is possible is preferable. The kneading temperature is a temperature at which all of mixed constituent components are melted, and usually from 160 to 250xc2x0 C., preferably from 180 to 240xc2x0 C. The kneading time can not be discussed in absolute terms since it depends on the kind and quantity of a mixed constituent component, and the kind of a kneading apparatus, and in the case of use of a kneading apparatus such as a pressure kneader, Banbury mixed and the like, the kneading time is usually from about 3 to 10 minutes. In the kneading process, constituent components may be kneaded in one time, and alternatively, a multi-stage divided kneading method can also be adopted in which a part of constituent components is kneaded, then, the remaining constituent components are added and kneaded.
As additive components to the olefin-based copolymer and thermoplastic resin composition used in the present invention, various stabilizers such as an antioxidant, ozone degradation inhibitor, ultraviolet ray absorber, light stabilizer and the like can be appropriately compounded. Further, additives such as an antistatic agent, slipping agent, internal releasing agent, coloring agent, dispersing agent, anti-blocking agent, lubricant, anti-fogging agent and the like can appropriately be compounded.
In the olefin-based copolymer and thermoplastic resin composition used in the present invention, there can be appropriately compounded fillers such as glass fiber, carbon fiber, metal fiber, glass bead, asbestos, mica, calcium carbonate, potassium titanate whisker, talc, aramide fiber, barium sulfate, glass flake, fluorine resin and the like, mineral oil-based softeners such as naphthene oil, paraffin-based mineral oil, and the like, as additive components.
In the olefin-based copolymer and thermoplastic resin composition used in the present invention, there can be appropriately compounded a flame retardant as an additive component. Examples of the flame retardant include inorganic compounds such as an antimony-based flame retardant, aluminum hydroxide, magnesium hydroxide, zinc borate, guanidine-based flame retardant, zirconium-based flame retardant and the like, phosphates and phosphorus compounds such as ammonium polyphosphate, ethylenebistris(2-cyanoethyl)phosphonium chloride, tris(tribromophenyl)phosphate, tris(3-hydroxypropyl)phosphine oxide and the like, chlorine-based flame retardants such as paraffin chloride, polyolefin chloride, perchlorocyclopentadecane and the like, bromine-based flame retardants such as hexabromobenzene, ethylenebisdibromonorbornanedicarboxyimide, ethylenebistetrabromophthalimide, tetrabromobisphenol A derivative, tetrabromobisphenol S, tetrabromodipentaerythritol and the like, and mixtures thereof.
The olefin-based copolymer and thermoplastic resin composition used in the present invention can also be used as a foamed body by compounding a foaming agent as an additive component. As specific examples of the foaming agent which can be suitably used for such foaming, there can be added main foaming agents such as sodium bicarbonate, ammonium bicarbonate, ammonium carbonate and the like, nitroso compounds such as N,Nxe2x80x2-dinitrosopentamethylenetetramine and the like, azo compounds such as azocarbonamide, azoisobutyronitrile and the like, benzenesulfonylhydrazine, p,pxe2x80x2-oxybis-(benzenesulfonylhydrazide), toluenesulfonylhydrazide, and sulfonylhydrazides such as toluenesulfonylhydrazide derivatives and the like. Further, a foaming aid can be appropriately used in the foaming processing. As specific examples of the foaming aid, examples thereof include salicylic acid, urea and compounds thereof, and the like.
When high frequency processing is required in the present invention, any polar polymer can be added. As specific examples of such a polar polymer, examples thereof include copolymers or multinary copolymers of ethylene with one or more comonomers selected from monocarboxylic acids such acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid and the like, dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid and the like and monoesters thereof, acrylates or methacrylates such as methyl methacrylate, methylacrylate, ethyl acrylate and the like, vinyl esters of saturated carboxylic acids such as vinyl acetate, vinyl propionate and the like, and ionomers thereof.
In the pressure-sensitive adhesive of the present invention, a pressure-sensitive adhesion imparting agent may also be added for the purpose of improvement of tack and for other purposes, though the pressure-sensitive adhesion imparting agent is not an essential constituent element. As the pressure-sensitive adhesion imparting agent, examples thereof include so-called tackifiers such as natural rosin resins such as rosin, dammar and the like, modified rosin and derivatives thereof, terpene-based resins and modified thereof, aliphatic hydrocarbon resins, aromatic hydrocarbon resins, alkylphenol resins, cumarone-indene resins and the like. Among them, terpenes such as terpenephenol, xcex1-polyterpene and the like are preferable compounds. Specifically, YS Resin TO-105, Clearon (these are manufactured by Yasuhara Chemical K.K.), Alcon, Estergum, Pencel (these are manufactured by Arakawa Kagaku K.K.), and the like are exemplified.
The pressure-sensitive adhesive of the present invention can also be used for a multi-layer laminate of two or more layers which has one layer comprising a layer composed of the pressure-sensitive adhesive of the present invention as the outermost layers or layer. In this laminate, materials constituting the layers may be mutually the same or different, and the materials constituting the layers can be selected from known thermoplastic resins other than the thermoplastic resin composition used in the present invention, rubber, and other components. Of these materials, the thermoplastic resin can be selected from various ethylene-based resins, various polypropylene-based resins, various polybutene-based resins, various polymethylpentene-based resins, polystyrene-based resins, copolymer resins of ethylene with acrylic monomers, copolymer resins of ethylene with vinyl acetate-based monomers, copolymer resins of ethylene with methacrylic monomers, acrylic resins, polyester-based resins, polycarbonate-based resins, nylon-based resins, polyvinyl alcohol-based resins and the like. As the rubber, examples thereof include ethylene/xcex1-olefin-based copolymer rubber, ethylene/xcex1-olefin/polyene-based copolymer rubber, styrene-based rubber, hydrogenated styrene-based rubber, diene-based rubber, known cross-linking rubber. Examples of other components include materials selected from woven fabric and non-woven fabric and the like, various stabilizers, various additives, fillers, mineral oil-based softeners, flame retardants, high frequency processing aids, rosin-based resins, polyterpene-based resins, synthetic petroleum resins, cumarone-based resins, phenol-based resins, xylene-based resins, isoprene-based resins and the like, and these can be appropriately compounded.
The method for producing the above-mentioned pressure-sensitive adhesive is not particularly restricted, and, for example, the adhesive can also be prepared in the form of a single layer sheet or film by dry-blending components or kneading components using a usual kneading apparatus, for example, a rubber mill, Brabender mill, Banbury mixer, press kneader, ruder, twin-screw extruder and the like, and then, subjecting the product to an inflation method, or extrusion method using a T die, single-screw drawing (extruding) method, twin-screw drawing (extruding) method, calender roll method and the like, or it can also be prepared in the form of a laminated sheet or film by adopting technologies such as co-extrusion, extrusion coating method (also referred to as extrusion laminate method) and the like using an inflation film producing apparatus or T die film producing apparatus and the like. The thickness of the resulting sheet or film is not particularly restricted, and preferably is from 0.001 to 5 mm, further preferably is from 0.005 to 2 mm.
The pressure-sensitive adhesive of the present invention may also be used as a pressure-sensitive sheet or film composed of a substrate and a pressure-sensitive adhesive layer. The substrate is not particularly restricted, and examples thereof include crystalline polypropylene, polypropylene-based resins obtained by homopolymerization of propylene or random or block-copolymerization of propylene with an xcex1-olefin, polyethylene-based resins of low density polyethylene, middle density polyethylene, high density polyethylene and linear low density polyethylene, poly-4-methyl-pentene-1-ethylene-xcex1-olefin copolymer, propylene-xcex1-olefin copolymer, ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, ethylene-n-butyl acrylate copolymer, and the like, providing they are thermoplastic resins. Further, mixtures of any combination of the above-mentioned resins can also be used. Among them, polyethylene-based resins or polypropylene-based resins having good compatibility with the olefin-based copolymer used in a pressure-sensitive adhesive layer are preferable from the standpoint that a composition having excellent flexibility, pressure-sensitive adhesion and scratch-resistance is effectively obtained. For giving pressure-sensitive adhesion between a pressure-sensitive adhesive layer and a substrate without inter-layer peeling, those comprising a pressure-sensitive adhesive layer and a substrate made of the same thermoplastic resin are preferable, and those show excellent recycling property. Further, the pressure-sensitive adhesion of a pressure-sensitive adhesive layer can be controlled by the blending ratio of an olefin-based copolymer and a thermoplastic resin used in the pressure-sensitive adhesive layer. If the content of a thermoplastic resin is increased in the blending system, its use as a substrate is also possible.
The above-mentioned substrate may be a single layer sheet or film, or may also be a composite sheet or film of two or more layers. The substrate may be colorless and transparent, however, the above-mentioned raw materials may also be subjected to coloration or printing before employed in various uses.
For obtaining the pressure-sensitive adhesive sheet or film of the present invention, a substrate layer and a pressure-sensitive adhesive layer can be prepared in the form of a laminated sheet or film by using technologies such as co-extrusion, extrusion coating method (also referred to as extrusion laminate method) and the like using an inflation film producing apparatus or T die film producing apparatus and the like. The thickness of the resulting sheet or film is not particularly restricted, and is preferably from 0.001 to 5 mm, further preferably is from 0.005 to 2 mm.
Further, when a pressure-sensitive adhesive sheet or film is used particularly as a wound article, it is possible, from the standpoint of drawing ability, and namely, self releasing property, to sandwich releasing paper, or to provide a coating of a releasing agent, for example, a silicone-based agent, such as an agent mainly composed of a long chain alkyl group adduct of polyethyleneimine, and the like, to further decrease affinity with its rear surface. Alternatively, it is possible to use various functional additives according to demands such as compounding of a releasing agent and other additives to improve lubrication property of the surface, and the like, within a range wherein the effect of the present invention does not deteriorate.
The pressure-sensitive adhesive obtained by the present invention can be suitably used as a pressure-sensitive adhesive sheet or film for packaging and casing, office and domestic use, electric insulation or identification, fixation or binding, repair and duct works, masking tape (sheet or film) or as a protective sheet or film for prevention of scratches in the transportation, storage and stacking from production to processing step, or in the prevention of scratches in secondary work in bending work and press work, of a stainless and aluminum plate as a construction material, a decorative laminated plate, a steel plate, a resin plate, glass, or domestic electric products, precise machinery, or an automobile body, as well as in other uses.
When the olefin-based copolymer used in the present invention and a thermoplastic resin composition containing this olefin-based copolymer is used as a hot-melt adhesive, it is suitably used for mutual adhesion of a polyolefin-based resin or adhesion of a polyolefin-based resin with a different material, or mutual adhesion of rubber or adhesion of rubber with a different material. As the rubber herein referred to, vulcanized rubber or non-vulcanized rubber is applied, and examples thereof include butyl rubber, isoprene rubber, butadiene rubber, ethylene propylene rubber, ethylene propylene diene rubber, styrene butadiene rubber, chloroprene rubber, natural rubber, acrylic rubber, olefin-based elastomer, styrene-based elastomer and the like. As the different material used, paper, cloth, leather, wood, various synthetic resins, metal, synthetic resin plate, decorative plywood, metal plate, coated steel plate, stone materials, glass and the like are exemplified.
As the adhesion method, various methods are applicable. For example, for adhering a polyolefin resin, adhesion methods generally used in hot-melt adhesion are useful such as a method in which the hot-melt adhesive of the present invention, which has been melted, is applied on the adhesion surface between a polyolefin resin molded article and another adhesion article, and immediately they are adhered under pressure. Alternatively, a method is useful in which a tape or sheet made of the hot-melt adhesion of the present invention is sandwiched between both adhesion articles, and they are melted for adhesion by a hot air furnace, heat press, high frequency and the like, as well as other methods. Likewise, for adhering vulcanized rubber, adhesion methods generally used in hot-melt adhesion are useful such as a method in which the hot-melt adhesive of the present invention, which has been melted, is applied on the adhesion surface between a vulcanized rubber molded article and another adhesion article, and immediately they are adhered under pressure. Alternatively, a method is useful in which a tape or sheet made of the hot-melt adhesion of the present invention is sandwiched between both adhesion articles, and they are melted for adhesion by a hot air furnace, heat press, high frequency and the like, as well as other methods. Further, in adhesion of non-vulcanized rubber, vulcanization and adhesion can be conducted simultaneously by a method in which the hot-melt adhesive of the present invention, which has been melted, is applied on the adhesion surface between a non-vulcanized rubber compound molded article and another adhesion article, and then, the temperature and the pressure required for vulcanization of rubber are applied. Alternatively, a method is useful in which a tape or sheet made of the hot-melt adhesion of the present invention is sandwiched between both adhesion articles, and the temperature and the pressure required for vulcanization of rubber are applied by a hot air furnace, heat press, high frequency and the like, as well as other methods.